Certain oxyalkylated derivatives of trinuclear aromatic compounds and method of making same



Patented May 27, 1952 CERTAIN OXYALKYLATED DERIVATIVES OF TRINUCLEAR A RO M A T I C COMPOUNDS AND METHOD OF MAKING SAME Melvin De Groote,University City, and Bernhard Keiser, Webster Groves, Mo., assignors toPetrolite Corporation, Ltd., Wilmington, Del., a corporation of DelawareNo Drawing. Application November 12, 1948, Serial No. 59,766

8 Claims. (Cl. 260-613) thetic products of the formula O(RaO),.HO(Ri),.H 0 R=0 ..H

in which R is a member of the class of alkyl, aralkyl, alicyclic andaryl radicals having not over 8 carbon atoms, and R1 and R2 are membersof the class of alkyl, aralkyl, alicyclic and aryl hydrocarbon radicalshaving not over 18 carbon atoms, and R3 is a member of the class ofethylene radicals, propylene radicals, butylene radicals,hydroxypropylene radicals, and hydroxybutylene radicals, and n is anumeral varying from 1 to 20, with the proviso that at least two molesof alkylene oxide be introduced for each phenolic nucleus.

Although the herein described products have a number of industrialapplications, they are of particular value for resolving petroleumemulsions of the water-in-oil type, that are commonly referred to as cutoil, roily oil, emulsified oil, etc., and which comprise fine dropletsof naturally-occurring waters or brines dispersed in a more or lesspermanent state throughout the oil which constitutes the continuousphase of the emulsion. This specific application is described andclaimed in our co-pending application Serial No. 59,765, filed November12, 1948, now Patent Number 2,543,489. The new products are also usefulas wetting, detergent and leveling agents in the laundry, textile anddyeing industries; ,as wetting agents and detergents in the acid washingof fruit; in the acid washing of building stone and brick; as wettingagents and spreaders in the application of asphalt in road building andthe like; as a constituent of soldering flux preparations; as aflotation reagent in the flotation separation of various aqueoussuspensions containing negatively charged particles, such as sewage,coal washing waste water, and various trade wastes and the like; ,asgermicides, insecticides, emulsifying agents, as, for example, forcosmetics,

spray oils, water-repellent textile finishes; as

lubricants, etc. 7 7

Attention also is directed to the fact that the herein describedcompounds may be employed as intermediates for the manufacture of morecomplex derivatives, for instance, they may be used as polyhydricalcohols combined with polycarboxy acids or their anhydrides, such asphthalic anhydride, with or without drying oil fatty acids, such aslinseed oil, fatty acid, to give resins or materials suitable for use inpaints and varnishes. Furthermore, this is true even though the averagevalue of n in the previously described formula is less than 2, forinstance, a trinuclear compound is treated with two to five moles of analkylene oxide, such as ethylene oxide, and particularly if it istreated with 3 moles, so as to yield a product of the followingcomposition:

own m O(C2H40)H ounruom u 2 R1 Such particular product is of distinctvalue for combination with such reactants, such as phthalic anhydride orlinseed oil fatty acid, to produce desirable paint and varnishconstituents.

If desired, one may consider the new materials or substances hereindescribed as hydrophile oxyalkylated phenol-aldehyde resins obtainedfrom oxyalkylation-susceptible, Water-insoluble, organicsolvent-soluble, fusible, phenol-aldehyde resins derived from certainmonofunctional and difunctional phenols in the ratio of two moles of amonofunctional and one mole of a difunctional phenol.

This application is a continuation-in-part of a number of our co-pendingapplications all of which were filed February 16, 1948, to wit: SerialNo. 8,722, now Patent Number 2,499,365; Serial No. 8,723, now PatentNumber 2,499,366; Serial No. 8,724, now Patent Number 2,499,367; SerialNo. 8,725, now Patent Number 2,581,367; Serial No. 8,726, now PatentNumber 2,499,368; Serial No. 8,727, now abandoned; Serial No. 8,728, nowabandoned; Serial No. 8,729, now abandoned; Serial No. 8,730, nowabandoned; Serial No. 8,731, now abandoned; Serial 'No. 8,732, nowabandoned; Serial No. 8,733, now abandoned, and Serial No. 8,734, nowPatent Number 2,501,015, which describe hydrophile oxyalkylated productsobtained.

by oxyalkylation of oxyalkylation-susceptible, water-insoluble, organicsolvent-soluble, fusible, phenolic resins including particularlyproducts derived from such phenol-aldehyde resins, and their use forvarious purposes, particularly demulsification.

It will be noted that in all of the foregoing co-pending applications wehave not attempted,

'for reasons which are perfectly obvious, to refer to a single specificcompound derived from a difunctional phenol and an aldehyde, such asformaldehyde. .The reason or reasons are obvious, to wit, theresinification may involve resin molecules having 3 to 7 or 10, or evenmore structural units. Numerous variations can take place, dependingupon whether ortho or para-phenols are used, and depending upon theparticular'aldehyde selected, on the particular catalyst selected,whether or not vacuum distillation isused as an after-step, etc.

In connection with the instant application, we are doing two thingswhich differentiate said invention from the various inventionspreviously described, and they are as follows:

(1) We are concerned with the product of a definite chemicalcomposition, and thus, claims are not concerned with describing theproduct in terms of method of manufacture, but the demulsifyingagent isdescribed in terms of structure only; and

(2) Instead of being derived solely, or substantially solely, fromdifunctional phenols, the herein described products are resin moleculesderived from monofunctional phenols and difunctional phenols, jointly,the ratio being two of monofunctional to one of difunctional. In all ourvarious aforementioned co-pending applications there is either no use ofa monofunctional phenol at all, or, if employed, it is only employed tomodify, i. e., prevent cross-linking in the instance of large-size resinmolecules, and particularly those derived totally or in part fromtrifunctional phenols. In brief, then, the present invention isconcerned with the breaking of petroleumemulsions by means ofoxyalkylated tri-nuclear'resins of the kind hereinafter described.

The preparation of tri-nuclear phenolic resins of known compositionwhich can be stated with specifity appears to be limited to formaldehydederivatives. Such resin molecules are tri-nuclear condensation products,are well known, and have been described in the literature.

These compounds are those which may be represented by the formula on 011OH H H R oo- .R

R1 R: R1

in which R is'a member of the class of alkyl, aralkyl, alicyclic andaryl radicals having not over 8 carbon atoms, and R1 and R2 are membersof the class of alkyl, aralkyl, alicyclic and aryl materials.

OH H OH H C C )3 H A B C D E l methyl.-. methyl... methyl.-. methyl...methyl. 2 tei-t-amyl tert-amyi tert-amyl tert-amyl tert- 1 amy. 3 tert-.do. tertnonyl.... mcnthyl.

butyl. octyl. 4 tert-amyl .do tert-amyl tert-amyl tert- 1 amy. '5methyl-.. methyl..- methyl..- methyl... methyl.

M01. Vt. 530 54 i 586 G00 612. ofCmpd.

F G H I I l tert-amyl tcrt-zunyl tcrt-amyl tert-amyl tert- I army 2terttert terttcrttertbutyl. butyi. butyl. butyi. butyl. do tert-amytertnohyl. mcuthyl.

octyl. do tertterttcrttertbutyl. but-yl. butyl. utyl. tert-amyl'tcrt-amyl tert-amyl tert-amyl tert- 1 amy. Moi. Wt. 614 628 670 G84696.

of Cmpd.

K L l\[ N O phenyl.-. phenyl... phenyl.-- phenyl. tertterttertte 5phenylln phenyl... phenyl... phenyl... phenyl Moi. W t. 738 752 794 S820.

P Q R S T cyclocyclocyclocyc1ocyclohexyl hexyl. hexyl. hexyl hexyl.octyl octyl. octyl..- ctyl-.. octyl.

terttertnonyl. menthyl. butyl. amyl. octyl. rttert- ..do tcrttertoctyl.octyl. octyl octyl. cyclocyclocyclocyclocyciohexyl. hexyi. hexyl hexyihexyl. 726 4 80G 820 73 2.

U V W X Y terttertterttertrtbutyl. butyl. butyl. butyl butyl nonyl.'nonyl. nonyl. nonyl. nonyi. tertterttertl do mcnth'yl.

butyl. amyl. octyi. nonyl nonyL... nony1 .do ncnyl.tertterttertterttertbutyl. butyl. butyi. butyl. butyl. .Mol. Wt. 6 740782 796 of Cmpd.

Having obtained a tri-nuclear'phenolic molecule or resin of the kinddescribed by the formula:

on OH on -oxyalkylation, particularly oxyethyl'ation. The

procedure employed is substantially' -the same as described in-variousoftheprecedlng-cm-pending 5 applications, particularly Serial No. 8,730and Serial No. 8,731, filed February 16, 1948.

Briefly stated, the process is essentially as follows: The trinuclearcompound or resin is mixed with a suitable amount of solvent, forinstance, about one-third or one-fourth its weight of xylene. Some othersolvent, such, as .cymene, or the like, can be employed. An alkalinecatalyst, such as caustic potash, caustic soda, sodium carbonate, sodiummethylate, or the like, is added. Our preference is to use approximately2.0% to 2.5% of sodium. methylate, based on the weight of thesolvent-free compound. The mixture of compound, solvent, and alkalinecatalyst (sodium methylate) is placed in a stirring autoclave andethylene oxide or any other selected alkylene oxide added, eithercontinuously or batchwise. For various reasons, our preferred alkyleneoxide is ethylene oxide. It will be noted that the present compounds arecharacterized by the addition of two to four moles of the alkylene oxideper phenolic nucleus. Thus, assuming uniform distribution, the previousformula can be rewritten as follows:

H R C- in which the various characters have their previous significanceand R3 is a member selected from the class of ethylene radicals,propylene radicals, butylene radicals, hydroxypropylene H C R Hradicals, and'hydroxybutylene radicals, and n is Example 1 530 grams ofa tri-nuclear compound of the kind characterized by the formula Apreceding, is mixed with 135 grams of xylene and 12 grams of sodiummethylate. The mixture is placed in an autoclave and 132 grams ofethylene oxide added. The temperature is raised to 150 to 160 C. Theautoclave is stirred rapidly during this period and the maximum pressureusually remains between 155 to 185 pounds per square inch. At the end ofapproximately 2 /2. to 4 hours the pressure is dropped to almost zero,particularly when the autoclave is cooled to room temperature. At theend of this period, the ethylene oxide is reacted completely so as togive a product having incipient hydrophile properties characterized bythe introduction of one mole of ethylene oxide per phenolic nucleus,based on average distribution. The reaction mass is subjected to asecond treatment of ethylene oxide in substantially the same manner soas to introduce an additional 132 grams of ethylene oxide. The procedureand conditions of operation, i. e., temperature, pressure, etc., aresubstantially the same as before. The final product obtained is a lightamber-colored fluid, having distinctly emulsifiable properties andhaving an average ratio of two for the character 1:. previously noted.

Example 2 The same procedure is followed as in Example 1, preceding,except that 4 additions of ethylene oxide are made under substantiallythe same op-' crating conditions so as to introduce a total of 528 gramsof ethylene oxide. The final product contains proportionately lessxylene and is somewhat lighter in colon-and is readily dispersible. Inthis instance, the value of n is 4.

Example 3 The same procedure is repeated as in the two.

preceding examples, except that the total amount of ethylene oxide addedis 792 grams in sixproportions of 132 grams each. If the addition ofethylene oxide tends to slow down during the final phase when the fifthand sixth additions are made, we have found it desirable to-cool thereaction vessel, add another five to six grams of sodium methylate, andthen start up again, go-v The same procedure is followed as in Example1, preceding, except that the trinuclear compound employed is C,preceding, and the amount employed is 586 instead of 530 grams.

Example 5 The same procedure is followed as in Example 1, preceding,except that the trinuclear com pound employed is F, preceding, and theamount employed is 614 grams instead of 530 rams.

' Example 6 The same procedure is followed as in Example 1, preceding,except that the trinuclear compound employed is G, preceding, and theamount employed is 628 grams instead of 530 grams.

Example 7 The same procedure is followed as in Example 1, preceding,except that the trinuclear compound employed is H, preceding, and theamount employed is 670 grams instead of 530 grams.

Example 8 The same procedure is followed as in Example 1, preceding,except that the trinuclear compound employed is H, preceding, and theamount employed is 794 grams instead of 530 grams.

Example 9 The same reactants and the same procedures were employed as inExamples 1 to 8, preceding, except that propylene oxide was used insteadof ethylene oxide in the same molar proportions, i. e., so the values ofn still represented 2, 4, and 6, based on average distribution. Theresultants, even on addition of the same molar amount'of propyleneoxide, have diminished hydrophile properties, in comparison with theresultants obtained with ethylene oxide. This illustrates the point thatpropylene oxide and butylene oxide give products of lower levels ofhydrophile properties than does ethylene oxide.

Example 10 The same reactants and the same procedures were employed asin Examples 1 to 8, preced- 7 mg, except athat sglycide was used:insteadzof ethylene oxide. :This :particular :reaction was conductedwith extreme :care and the glycide added in only small :amountsrepresenting :a fraction rof a imole. The ;reaction was stopped when twomoles of :glycidewereaddedper mole of phenolic nucleus. We are extremelyhesitant to suggest even the experimental use of glycide andmethylglycide, for the reason that 'disastrous --resultscan be obtained,even in experimentation with laboratory'quantities. -WeJhave foundnd-"advantage to be obtained, particularly from lthe -economic'standpoint, in any of the oxides other than ethylene oxide, andpropylene oxide. We have found no genuine advantage Tfrom "the use ofpropylene oxide over and above ethylene oxide. Ethylene :oxide isdefinitely our preferred and the most "advantageous oxyalkylating agent.

Jf desired. oxyalkylati'on,particularly oxyethylation, can be conductedwithout theuse of a -solvent. All that is required is that thephenoliccompound be a liquid at the'temperatureOf-"OXyethylation, forinstance, between l-fill to 200 C. If -a-:solvent is employed, thereisno objection iJ-to the solvent being presentin the final product formany uses, and Particularly for demulsification. If desired, of course,products exemplified .by previous examples to wit, Examples .l to 10,inclusive, maybe-sum jected to distillation, particularly vacuum.distillation, to remove the-solvent, such as xylene; for instance, wehave found that raising the temperature to 150 C. under a vacuum in 25mm. of mercury removes-the xylene readily.

The instant application is concerned with certainaoxyalkylatedderivatives of trinuclear compounds. it is obvious that the :alicycl-icanalogues derived by nuclear hydrogenation are equally serviceable forthis purpose, and particularly, as intermediates for the manufactureof'more complex compounds for use as demulsifying agents. In a generalway, conversion of the aromatic'material to an'alicyclic materialfollows either one of two procedures; one can hydrogenate the resin in aconventional manner, followed by oxyalkylation of the hydrogenated resinin substantially the same manner 'as is employed in .the case of thenonhydrogenated resin. The second procedure is to hydrogenate theoxyalkylated derivative, rather than the resin itself. As an example ofsuch procedure, .referenceis -made to our copending application SerialNo. 726,201, .filed February 3,1947, now abandoned.

Having thus described our invention, what we claim as new and desire tosecure by Letters Patent is:

in A which is a member of the class 'of alkyl,

aralkyl, i'alicyclic and aryl radicals .having .not over 8 carbon atoms,and-R1 -and R2 sare-zmembers of the class of alkyl, aaral'kyl,al-icyclic -and aryllhydrccarbon radicals :having not .over 118 carbon:atoms, and .TRs is a member :of Et'he :class of ethylene :radicals,propylene radicals, abutylene :radicals, lhydroxyp'ropylene :radicals,:and hydroxybutylene radicals, and is ca :numeral varying. from .1 to:20, with the :proviso that-lat least :2 moles of .alkylene :oxide :beiintroduced for each phenolic nucleus.

-2. Hydrophile synthetic formula:

in which.2R:is azmemberiof the-.classmfaalhyl, ara'lkyl, 'alicyclic and.aryl radicals z'having :not over 8 :carbon: atoms,..and R1 and 1R2:are-rmembers of the class of alkyl, aralkyl, alicyclici-and arylhydrocarbon radicals having not over 18 carbon atoms, and n is a numeralvaryingfrom l to 20, with the proviso that at least 2 moles of ethyleneoxide be introduced for each phenolic nucleus.

3. The'product of claim 2, wherein .n is not greater than 6.

4. .-The product ofcla-im'2, wherein m'isinot greaterthan' 6 and allnuclear substituentlhydrocarbonura-dicals are a'llryl.

,5. The product of claim .2, wherein-n -is-.not greater than 1 Sand allnuclear substituent. hydrocarbon radicals are alkyl radicals having atleast 4 and:not morethan's carbonatoms.

.6. ,The'product'of claimi2, wherein '12. is not greater I than '6 andall nuclear substituent hydrocarbon radicals are alkyl. radicalsrhaving4 products of :the

to 8 carbon atoms, with the added proviso that there is at least oneoccurrence of a butyl radical.

'7. The product of claim 2, wherein n is not greater than 6 and allnuclear substituent hydrocarbon radicals are alkylradicalszhaving 4 to18 carbonatoms. with the added :proviso that there is :at least oneoccurrenceof :an -amyl radical.

8. The product of claim 2, wherein n is not greater than 6 andall'nuclear substituent hydrocarbon radicals l are alkyl radicals having:4 to 8 carbon atoms, with :the i added proviso that there is: at leastone occurrence of a butyl radical.

MELVIN DE l GROOTE. BERNHARD KEISER.

REFERENCES CITED The following references are (if-recordintho file ofthis patent:

UNITED. STATES PATENTS Number Name :JDate 72,430,002 :De .Groote .et1al.Nov.-'?4,:194.=7 12,454,541 .Bockxet' al. l Nov. 23,1948 2,450,272Doelling :et'al. Sept;- 28, -1948 2,501,015 Wirtel Mar. .21, 11-950

1. HYDROPHILE SYNTHETIC PRODUCTS OF THE FORMULA